Method of preparing poly (hydroxy-ethers) based polyesters



United States Patent U.S. Cl. 260-47 5 Claims ABSTRACT OF THE DISCLOSUREThe invention relates to novel linear thermoplastic poly (hydroxy-ether)polyesters having relatively high molecular Weights and suitable forcoating, laminating, film making and molding, prepared by reacting analicyclic dicarboxylic acid halide with a poly (hydroxyether) prepolymerin the presence of an acid accepting agent and a basic catalyst.

This invention relates to novel poly(hydroxyethers) based thermoplasticpolyesters and to a method for their preparation. More particularly,this invention relates to novel thermoplastic polyesters which haverelatively high molecular weights and are prepared by reacting dibasicacid halides defined hereinunder with poly (hydroxyethers) definedhereunder and are characterized by having excellent heat distortionstabilities, impact resistances and desiredphysical properties of highmolecular weight poly (hydroxyethers) resins derived from bisphenols andepihalohydrins.

Thermoplastic poly(hydroxyethers) resins are known in the art and aredisclosed well in the patent literatures including Japanese patentpublication No. 20,988/ 63, 1,840/64. And the poly(hydroxyethers) resinsare prepared by a method conducted by admixing a bisphenol and about onemole of an epihalohydrin or a diglycidyl ether of bisphenol, per mole ofbisphenol, together with an alkali metal hydroxide, generally in anaqueous medium 'at a temperature of about 20 C. to boiling or reflux,but it is difficult to prepare a poly(hydroxyether) resin which has asufiiciently high'molecular weight and a substantially linear structurefor the methods have the defects described hereinunder:

(1) While it is necessary for obtaining linear polymer to carry out thereaction at atemperature below 50 C., it is ditficult to accomplish thereaction and to obtain high molecular weight polymers by carrying outthe reaction at a temperature below 60 C.

(2) While it is necessary for the growth of the polymer in molecularweight to carry out the reaction at a temperature above 60 C., not onlythe desired reaction summarized in the following Equation 1 but also thebranching reaction occur considerably at a temperature above 60 C.,

wherein 1, A X, G, h, i, j and m have the same significance as definedhereinunder; v and z represent whole numbers greater than one, and thebranching reaction is described in many literatures including theJournal of Polymer Science Part A, vol. 2, pages 2,631 to 2,645 (1964).Therefore, in the case that one wants to get a linear poly(hydroxyether) resin having high mel-t index by the known methods, aresin having poor thermal stability and poor physical strength isobtained. On the contrary, in the case that one wants to get arelatively high molecular weight poly(hydroxyether) resin havingphysical strength, one gets a resin having high resistance to flow orcontaining gel.

The well-known poly(hydroxyether) resins have a Melt Index of from about0.3 to about 3 gr./10 mm. (according to ASTM test designation D-1,238procedure at 220 C., under 44 p.s.i.), Heat Distortion Temperature ofabout 86 to about 91 C. under 66 p.s.i. and of about 80 to about 86 C.under 264 p.s.i. (according to ASTM test designation D648 procedure),notched Izod impact strength of about 2 to about 5 ft. 1b./in. (notch)according to ASTM test designation D-256 procedure), un-

notched Izod impact strength of about 60 to about ft. lb./in. (2.5"),Flexural strength of about 14,000 to about 17,000 p.s.i. 10 tensilemodulus of about 3.3 to about 3.5 p.s.i. 10 and volume resistivity ofabout 4 to about 5 ohm-cm. x 10 )m )m R R alirlgag in}Cantata CHR"HO-C-R' rt; rlEilOH L JhL Jil- J1 preparing a novel thermoplasticpoly(hydroxyether) based polyester having sufficiently high molecularWeight.

A particular object of this invention is to provide a method forpreparing a poly(hydroxyether) based polyester which is comparable topolycarbonate in the heat distortion temperature and in the notched Izodimpact strength and also is comparable to poly(hydroxyether) resin in anumber of the excellent properties of the poly (hydroxyether) resinwhich are shown heretofore.

Further object of this invention is to provide a novel thermoplasticresin having excellent physical and chemical properties suited forcoating, laminating, film making and molding.

Another object of this invention is to provide a novel thermoplasticresin for preparing coating, lamination or film having low gaspermeability.

The poly(hydroxyethers) based polyesters of this invention are,essentially, linear condensation products of the dibasic acid halidesdefined hereinunder and the poly (hydroxyethers) prepolymers which are,essentially, disclosed hereinunder.

And the poly(hydroxyethers) based polyesters of this invention contain,essentially, structural units of following formulas:

and the polyester of this invention has an average composition whichcomforms to and may be represented typically by the following formula:

(wherein J, A R, R", G, Z, h, i, y, m and p have the same significanceas defined hereinunder; v represents a whole number greater than one,ranges preferably 2 to 19; w represents a whole number greater thanone.)

The method of this invention, for preparing the poly (hydroxyethers)based polyesters, comprises essentially, condensing (A) apoly(hydroxyether) prepolymer (1) containing two terminal phenolichydroxyl groups with (B) a dibasic acid halide (II) represented by thefollowing general formula (1) in the presence of (C) a strongly basiccompound (III), e.g. an alkali metal hydroxide, as an acid acceptant and(D) a catalytic amount of basic catalyst (IV) at a suitable temperature,preferably at about C. to about 50 C.; said poly(hydroxyether)prepolymer (I) is prepared by reacting (A-l) a molar excess amount ofbisphenol (a) with (A-2) an epihalohydrin (b) defined hereinunder inone, two or more steps H/ rillta,rostz uo rlnltiatoorolzrolcol (I) tosaid dibasic acid halide is preferably in the proportion of from 0.985to 1.015 of phenolic hydroxyl groups of said poly(hydroxyether)prepolymer (I) per about one COX group of said dibasic acid halide (II),where COX has the same significance defined in the Formula 1; the ratioof said strongly basic compound (III) to said poly(hydroxyether)prepolymer (I) is in the proportion of one or more than one equivalentweight of base per one equivalent phenolic hydroxyl group of saidpoly(hydroxyether) prepolymer (I).

The dibasic acid halides (II) used for preparing the poly(hydroxyethers)based polyesters of this invention are represented by the followinggeneral Formula 1, and the term dibasic acid halides (11) used in thisspecification means acid dihalides, bishaloformates and mixture thereofwhich are represented by the general Formula 1:

LR'I fifii lLijr l LT J LJuL .LLJr

wherein L is a hydrocarbon residue selected from the group consisting ofaromatic hydrocarbon residues and alicyclic hydrocarbon residues; A is amember selected from the group consisting of:

(1) the divalent groups D where -D-- is a divalent aliphatic hydrocarbonresidue of up to six carbon atoms; (2) the divalent groups DE where D-has the same significance defined heretofore and E is an atom selectedfrom the group consisting of O and S; (3) the divalent groups DED whereD- and E have the same significance defined heretofore; (4) O; (5) S;(6) SO (7) OCOO and (8) CO-;

R is a divalent aliphatic hydrocarbon residue attached directly to ringcarbon of L; G represents a halogen atom or alkyl group; m ranges zeroto a whole number of replaceable hydrogens substituted on thehydrocarbon residue; q and r range zero to one; s and t range zero toone, however s+t range one to 2; W ranges zero to one, however, when sis zero, W must be zero and when s+t is one, u must be zero; p' rangeszero to one.

The poly(hydroxethers) prepolymers (I) used for preparing the poly(hydroxyethers) based polyesters of this invention have an averagecomposition which comforms to and may be represented typically by thefollowing Formula 2:

wherein h, i and j range zero to one, however h+j ranges one to two; Iis an aromatic divalent hydrocarbon radi cal such as naphthylene andphenylene with phenylene being preferred for purposes of this invention;G is alkyl radical such as methyl, n-propyl, n-butyl, n-hexyl, n-octyland the like, preferably alkyl radical having a maximum of 4 carbonatoms; or halogen atom, i.e., chlorine, bromine, iodine, or fluorine.

It is to be understood that whenever there are substituents exclusive ofthe hydroxyl groups on either or both of the aromatic divalenthydrocarbon groups, that these substituents can be the same ordifierent; m is an integer having a value of from 0 to a maximum valuecorresponding to the number of hydrogen atoms on the aromatic ring (J)with which can be replaced by substituents and can have the same ordifferent values; and A is a divalent radical, as for example or O, or--S-, or SO-, or -SO or a divalent hydrocarbon radical as, for example,an alkylene radical such as methylene, ethylene, trimethylene,tetramethylene, pentamethylene, hexamethylene, 2-ethy1 hexamethylene,octamethylene, nonamethylene, decamethylene, and the like; an alkylideneradical such as ethylidene, propylidene, 'isopropylidene, isobutylidene,amylidene, isoamylidene, l-phenyl ethylidene and the like, or acycloaliphatic radical, such as 1,4-cyclohexylene, 1,3-cyclohexylene,cyclohexylidene, and the like, or halogenated alkylidene, al-klene orcycloaliphatic radicals, alkoxy and aryloxy substituted alkylidene,alkylene or cycloaliphatic radicals, such as methoxy methylene, ethoxymethylene, ethoxy ethylene, 2-ethoxy trimethylene, 3-ethoxypentamethylene, 1,4-(Z-methoxycyclohexane), phenoxy ethylene, 2-phenoxytrirnethylene, 1,3-(2-phenoxy cyclohexane), and the like, aralkyleneradicals, such as phenyl ethylene, 2-phenyl trimethylene, l-phenylpentamethylene,

2 -phenyl decamethylene, and the like, aromatic radicals,

dodecylphenylene) and the like; or A can be a ring which is fused to oneof the J groups as is the case, for example, in the compound having theformula:

or A can be a radical containing a silicon atom as, for example,dimethylsiloxy, diphenylsiloxy, methylphenylsiloxy and the like.

Particularly preferred are the dihydric polynuclear phenols having thegeneral formula:

( 3; an. b

wherein G, is as previously defined, m has a value of from 0 to 4inclusive and A is an alkylene or alkylidene group,

preferably having from 1 to 3 carbon atoms inclusive or A is a saturatedgroup having the formula:

Poly(hydroxyethers) produced using the dihydric polynuclear phenolsdescribed in the preceding paragraph have extremely good mechanicalproperties. In addition poly- (hydroxyethers) produced using a dihydricpolynuclear phenol wherein A is a saturated group having the forhaveheat distortion temperatures which are relatively high.

Exemplary of other specific dihydric phenols include among others thebis-(hydroxyphenyD-alkanes such as 2,2-bis-(p-hydroxyphenyl)-propane,commonly referred to as bisphenol-A, 2,4-dihydroxy diphenylmethane,bis-(2- hydroxyphenyl) methane, bis-(4-hydroxyphenyl)-methane, bis (4hydroxy 2,6-dimethyl-3-methoxyphenyl)- methane, 1,1-bis-(4-hydroxypheny1)ethane, 1,2-bis-(4- hydroxyphenyl) ethane, 1,1 bis(4 hydroxy 2 chlorophenyl) ethane, 1,1 bis (3,5dimethyl-4-hydroxyphenyl)-ethane, 1,3 bis (3 methyl 4hydroxyphenyl)propane, 2,2 bis (3 phenyl 4 hydroxyphenyl) propane, 2,2bis (3 isopropyl-4-hydroxyphenyl)-propane, 2,2 bis (2 isopropyl4-hydroxyphenyl) propane, 2,2-bis-(4-hydroxy-naphthyl)-pr0pane, 2,2bis-(4-hydroxyphenyl)-pentane, 3,3-bis-(4-hydroxyphenyl) pentane,2,2-bis-(4-hydroxyphenyl)-heptane, bis (4 hydroxyphenyl) phenylmethane,bis (4 hydroxyphenyl) cyclohexylmethane, 1,2 bis-(4-hydroxyphenyl) 1,2bis (phenyl) propane, 2,2 bis-(4- hydroxyphenyl) 1 phenylpropane and thelike; dihydroxybiphenyls such as 4,4 dihydroxybiphenyl, 2,2-dihydroxybiphenyl, 2,4 dihydroxybiphenyl and the like; di(hydroxyphenyl)sulfones such as his (4 hydroxyphenyl)-sulfone, 2,4 dihydroxydiphenylsulfone, 5 chloro 2,4 dihydroxydiphenyl sulfone, 5-chloro-4,4-dihydroxydiphenyl sulfone, 3'-chloro-4,4'-dihydroxydiphenyl sulfoneand the like; di(hydroxyphenyl) ethers such asbis-(4-hydroxyphenyl)-ether, the 4,3'-, 4,2-, 2,2-, 2,3'-, dihydroxydiphenyl ethers 4,4 dihydroxy-2,6-dimethyldiphenyl ether,bis-(4-hydroxy-3-isobutylphenyl)- ether, bis (4hydroxy-3-isopropylphenyl)-ether, bis-(4- hydroxy 3 chlorophenyl) ether,bis (4 hydroxy- 3 fluorophenyl) ether, bis (4 hydroxy 3 brornophenyl)ether, bis (4 hydroxynaphthyl) ether, bis- (4 hydroxy 3 chloronaphthyl)ether, bis (2 hydroxybiphenyD-ether, 4,4-dihydroxy 2,6 dimethoxydiphenylether, 4,4 dihydroxy 2,5 diethoxydiphenyl ether, and the like; alsosuitable are 1,1-bis-(4-hydroxyphenyl) 2 phenylethane,1,3,3-trimethyl-1-(4-hydroxyphenyl) 6 hydroxyindane, 2,4 bis (phydroxyphenyl) 4 methylpentane and the like.

The epihalohydrins (b) which can be used for preparing thepoly(hydroxyethers) prepolymers (I) are represented by the followinggeneral Formula 4, and the term epihalohydrins (b) used in thisspecification means the compounds and mixture thereof represented by thefollowing Formula 4:

RI RI! X-CH2(|)--(|3H wherein R and R" which can be the same ordifferent are hydrogen or methyl and X is a halogen atom, i.e.,chlorine, bromine, and the like. Specific epihalohydrins areepichlorohydrin, epibromohydrin, 1,2 epoxy 1- methyl 3 chloropropane and1,2-epoxy-2-methyl-3- chloropropane. The examples of methods forpreparing the poly(hydroxyethers) prepolymers (I) include, but are notlimited to, the following methods:

(1) A method reacting a bisphenol (a) with from about 0.70 to about 0.95moles, preferably from about 0.75 to about 0.90 moles, of anepihalohydrin (b), per mole of the bisphenol (a),

(2) A method reacting a dihalohydrin ether which is prepared by reactinga bisphenol (a) with a molecular excess amount of epihalohydrin (b), andhas the following Formula 2-1:

R n G)... a R R taacaoiilt. 1L. lo CH. 3 3H I L Jh L Lia L Jr I I i (|)HOH X where various letters have the same significance definedheretofore), with from about 1.1 to about 2.0 moles, preferably fromabout 1.2 to about 1.6 moles, of bisphenol (a) per mole of thedihalohydrin ether,

(3) A method reacting diglycidyl ether which is prepared by reacting abisphenol (a) with a molar excess amount of epihalohydrin (b), and hasthe following Formula 2-2:

(Where various letters have the same significance defined heretofore)with from about 1.1 to about 2.0 moles, preferably from about 1.2 toabout 1.6 moles, of bisphenol (a), per mole of the diglycidyl ether,

(4) A method reacting a molar excess amount of bisphenol (a) withepihalohydrin (b) and the dihalohydrin ether described above or (and)diglycidyl ether described above.

The method (1), (2) and (4) are conducted by admixing from one or morethan one equivalent amount of base, e.g. sodium hydroxide, potassiumhydroxide, per equivalent amount of reactive halogen atoms contained inthe epihalohydrin (b) and dihalohydrin ether with the materialsindicated above.

And a catalyst can be used, if necessary, and in those methods (1) to(4) basic catalysts are preferable and the preferred among them includethe basic catalysts (IV) defined in this specification. For an example,the process by which the poly(hydroxyethers) prepolymers (I) whichis'suitable for preparing gel-free thermoplastic poly(hydroxyethers)based polyesters of this invention is conducted by admixing a bisphenol(a), from about 0.70 to about 0.95 moles of epihalohydrin (b), per moleof the bisphenol (a), together with from about 1.1 to about 1.2 moles,per mole of the epihalohydrin (b), of alkali metal hydroxide such assodium hydroxide, potassium hydroxide and the like, generally in anaqueous medium at a temper'ature of about C. to about 80 C.

Careful control of the ratio of phenolic hydroxyl groups to reactivehalogen atoms or (and) epoxy groups in the starting materials is ofgreat importance in order to obtain a final product having the desiredcharacteristics such as small resistance to flow and high chemicalresistance. For example, in the case that the process is carried with areaction mixture containing more than 0.96% epoxy group per one phenolichydroxyl group, it is necessary for accomplishing the reaction to carryat higher temperature and for longer time, and it is inevitable toobtain the poly(hydroxyether.) having too high molecular Weight andbranched structure. And it is very difiicult to accomplish the reactionof such a high molecular weight p0ly(hydroxyether) with a dibasic acidhalide (H) 'without causing any branching or crosslinking reaction, sothe product having sufiicient physical strength and chemical resistanceand good thermoplasticity cannot be obtained. In the case that theprocess is carried with a reaction mixture containing less than 0.66epoxy group per one phenolic hydroxyl group, for an example, thereaction product having too small molecular weight or the mixture ofhydroxylether and unreacted bisphenol (a) is obtained And the finalpolymer prepared by condensing such a reaction product with a dibasicacid halide (II) has small Melt Index and poor chemical resistance forthe polymer contains too much COO bonds.

The dibasic acid halides (H) which are useful for preparing thepoly(hydroxyethers) based polyesters of this invention include, but arenot limited to,

(1) Acid dihalides of aromatic dicarboxylic acids (III-1) represented bythe following general Formula (2) Acid dihalides of alicyclicdicarboxylic acids (II- 2) represented by the following general Formula1-2,

(3) Other acid dihalides of dicarboxylic acid (II-3) represented by thefollowing general Formula 1-3,

(4) Bishalformates of dihydric phenols (II-4) represented by thefollowing general Formula 14, v

(5) Bishaloformates of dihydric alcohols (1L5) rep L' J -l-a) wherein Aris a member selected from the group comprising of m-phenylene group,p-phenylene group, 1,5- naphthylene 1 group, 2,6-naphthylene group, thegroups which are derived by substituting them with halogen atom or (and)alkyl groups; X is selected from the group consisting of chlorine atomand bromine atom; CO+ is a carbonyl group, XCO is a haloformyl groupattached directly to an aromatic ring carbon; Y is a substituted halogenatom; m ranges zero to 4, and examples of the acid dihalides of thearomatic dicarboxylic acids (II-l-a) having the Formula l-l-a include,but are not limited to, the acid dichlorides and the acid dibromides ofthe followingacids: terephthalic acid, iso-phathalic acid,1,4-dicarboxyl 2 chlorobenzene, 1,4-dicarboxyl-2,5-dichlorobenzene,1,4-dicarboxyl 2,3,5,6 tetrachlorobenezene, 1,S-dicarboxylnaphthalene,2,6-dicarboxylnaphthalene, 2,7-dicarboxylnaphthalene and the like.

Another class of acid dihalides of aromatic dicarboxylic acids (II-l-b)having the Formula 1-1 and preferably useful for the preparation ofpoly(hydroxyethers) based polyesters of this invention are those of thefollowing general Formula l-l-b):

wherein A is a member selected from the group consisting of alkylidenegroups of up to six carbon atoms, other alkylene groups of up to sixcarbon atoms, aliphatic glycol residues: OC11H O-- where n ranges from 2to 6, aliphatic thioglycol residue: YS--C H where n ranges from 2 to 6,-O, -S, --SO OCOO- and CO; X is selected from the group consisting ofchlorine atom and bromine atom;

is selected from the group comprising of m-phenylene group, p-phenylenegroup and the groups which are derived by substituting them with alkylgroups; G represents a substituted halogen atom; m ranges zero to 4; uranges zero to one, and examples of the acid dihalides of dicarboxylicacids (II-l-b) having the formula (1- l-b) include, but are not limitedto, the acid dichlorides and the acid dibromide of the following acids:

4,4 dicarboxybiphenyl, 3,3 dicarboxybiphenyl, 1,1- bis(4 carboxyphenyl)methane, 1,1 bis (4 carboxyphenyl) ethane, 2,2 bis(4 carboxyphenyl)propane, 1,4 bis(4 carboxyphenyl) butane, 1,2 bis(4 carboxyphenoxy)ethane, 1,3 bis(4 carboxyphenoxy)- propane, 1,2 bis(4 carboxy phenothio)ethane, 1,4- bis(4 carboxyphenoxy) butane, 1,5 bis(4 carboxyphenoxy)pentane, 1,6 bis(4 carboxyphenoxy) hexane, bis(4 carboxyphenyl) ether,bis(4 carboxyphenyl) thioether, bis(4 carboxyphenyl) sulfone, 4-carboxyphenoxy 4' carboxyphenyl methane, 4,4 dicarboxybenezophenone andthe like.

One class of acid dihalides of alicyclic dicarboxylic acids (II-2)having the above general Formula 1-2 and preferably useful for thepreparation of the poly(hydroxyethers) based polyesters of thisinvention are those of the Formula 1-2-a:

I- (G)... r (on.

A]. oo x wherein A, X, G and m have the same significance definedheretofore;

is a member selected from the group comprising of 1,4-

cyclohexylene groups and the groups which are derived by substitutingthem with alkyl groups is preferably trans- 1,4-cyclohexylene group; uranges zero to one, s ranges zero to one, when s is zero, however, amust be zero, and the examples of the acid dihalides of alicyclicdicarboxylic acids (II2a) having the Formula 1-2-a include, but are notlimited to, trans-hexahydroterephthaloyl chloride, hexahydroisophthaloyl chloride, hexa'hydrophthaoyl chloride, hexahydroiso-phthaloylchloride trans-trans- 4,4' dodecahydrodibenzoyl chloride, cis-trans 4,4-dodecahydrodibenzoyl chloride, cis-cis 4,4 dodecahydrodibenzoylchloride, 3,3 dodecahydrodibenzoyl chloride, 2,2 dodecahydrodibenzoylchloride, the acid dibromides corresponding to them and the like.

Examples of other acid dihalides of alicyclic dicarboxylic acids (II-2)having the general Formula l-2 include, but are not limited to, the aciddichlorides and the acid dibromides of the following acids:3,3'-dodecahydrodibenzoic acid, 2,2-dodecahydrodibenzoic acid,trans-cyclopropane-1,2-dicarboxylic acid,trans-3-methyl-cyclopropane-1,2-dicar-boxylic acid,trans-cyclobutane-l,3 dicarboxylic acid, cyclopentane-l,3-dicarboxylicacid, cis-cyclopropane-l,Z-dicarboxylic acid,cyclobutane-l,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acidand the like.

One class of the acid dihalides of dicarboxylic acid (II-3) having thegeneral Formula (1--3) which are useful for preparing thepoly(hydroxyethers) based polyesters of this invention are those of thefollowing Formula (l-3-a):

wherein is a member selected from the group comprising of pphenylenegroup, m-phenylene group, 1,4-cyclohexylene group, 1,3-cyclohexylenegroup, and the groups which are derived by substituting them with alkylgroups; G is a substituted halogen atom; m ranges zero to 4; q and rrange one to 3; X has the same significance defined heretofore; and theexamples of the acid dihalides of dicarboxylic acids (II3-a) having thegeneral Formula (l-3-a) include, but are not limited to, the following:p-phenylene diacetyl chloride and p-phenylene dipropionyl chloride,p-hexahydrophenylene diacetyl chloride, the acid dibromidescorresponding to them and the like.

Another class of the acid dihalides (II-3) having the general Formula(1-3) which are useful for preparing the poly(hydroxyethers) basedpolyesters of this invention are those of the following Formula (l-3-b):

wherein is a member selected from the group comprising of pphenylenegroup, m-phenylene group, 1,4-cyclohexylene group and the groups derivedby substituting them with alkyl groups; B, X, Y, m and u have the samesignificance defined heretofore; q and r range one to 3; and theexamples of the acid dihalides (II-3-b) having the above Formula (1-3b)include, are not limitied to, the following:

the acid dibromides corresponding to them and the like.

One class of the bishaloformates of dihydric phenols (II-4) having thegeneral Formula (1-3) and being preferably useful for preparing thepoly(hydroxyethers) based polyesters of this invention are those of thefollowing Formula (1-4-a):

wherein J is a member selected from the group comprising of phenylenegroups, (preferably p-phenylene group, mphenylene group), naphthylenegroups (preferably 1,5- naphthylene group, 2,6-naphthylene group), thegroups which are derived by substituting them with alkyl groups; A, X,G, In and u have the same significance defined heretofore. And theexamples of the bishaloformates of dihydric phenols '(II4b) having theFormula (2-4-17) include, but are not limited to the bischloroformatesand bisbromoformates of the following dihydric phenols: resorcinol,hydroquinone, 1,S-dihydroxynaphthalene, 2,6-dihydroxynaphthalene,2,7-dihydroxynaphthalene, and the like.

Another class of the bishaloformates of dihydric phenols (II-4) havingthe general Formula 1-4 and being preferably useful for the preparationof the poly(hydroxylethers) based polyesters of this invention are thoseof the following Formula (1-4-b):

wherein J is a member selected from the group comprising of phenylenegroups (preferably p-phenylene group, mphenylene group), naphthylenegroups (preferably 1,5-

naphthylene group, 2,6-naphthylene group, 2,7-naphthyl ene group) andthe groups which are derived by substituting them with alkyl groups; A,X, G, In and u have the same significance defined heretofore. And theexamples of the bishaloformates of dihydric phenols (II-4- b) having theabove Formula 2-4-b include, but are not limited to, thebischloroformates and bisbromoformates of the following dihydricphenols:

and the like;

di(hydroxyphenyl)sulfones such as bis (4-hydroxyphenyl) -sulfone,5-chloro-4,4'-dihydroxydiphenyl sulfone, 3'-chloro-4,4-dihydroxydiphenyl sulfone and the like;

di(hydroxyphenyl ethers such as bis- 4-hydroxyphenyl -ether,

the 4,3-dihydroxy-diphenyl ethers, 4,4'-dihydroxy-2,6-dimethyldiphenylether, bis-(4-hydroxy-3-isobutylphenyl)-ether,bis-(4-hydroxy-3-isopropylphenyl)-ether,bis-(4-hydroxy-3-chlorophenyl)-ether,

bis- 4-hydroXy-3-fluorophenyl) -ether,

bis- (4-hydroxy-3-bromophenyl) -ether,

bis- 4-hydroxynapthyl -ether, bis-(4-hydroxy-3-chloro-napl1thyl) -ether,4,4-dihydroxy-2,6-dimethoxydiphenyl ether,4,4-dihydroxy-2,S-diethoxydiphenyl ether,

and the like; also suitable are1,1-bis-(4-hydroxyphenyl)-2-phenylethane, 2,4-bis(p-hydroxyphenyl)-4-methylpentane and the like.

Examples of other bishaloformates of dihydric phenols (II-4-b) havingthe general Formula 2-4-b include, but are not limited to, thebischloroformates and bisbromoformates of the following dihydricphenols:

2,4'-dihydroxydiphenylmethane, 2,2'-dihydroxybiphenyl,2,4-dihydroxybiphenyl, 2,4-dihydroxydiphenylsulfone,5'-chloro-2,4'-dihydroxydiphenylsulfone, 4,2'-dihydroxydiphenylether,2,2'-dihydroxy-diphenylether,

2,3 '-dihydroxy-diphenylether and the like.

One class of the bishaloformates of dihydric alcohols '13 (II-) havingthe general Formula 1-5 and being useful for preparing thepoly(hydroxyethers) based polyesters of this invention are those of theFormula 1-5-a:

"(Gin wherein is a member selected from the group comprising apphenylene group, m-phenylene group, 1,4-cyclohexylene group,1,3-cyclohexylene group and the groups which are derived by substitutingthem with alkyl groups; X has the same significance defined heretofore;G is a substituted halogen atom; m ranges zero to 4; q and r range fromzero to 3, when 1,4-bis (2-hydroxyiso-propyl) -benzene,1,3-bis(2-hydroxyethyl) -benzene, 1,3-bis (2-hydroxypropyl) -benzene,1,3- bis(2-hydroxyiso-propyl)-benzene and the like.

' Another class of the bishaloformate of dihydric alcohols (II-5) havingthe general Formula 1-5 and being useful for preparing thepoly(hydroxylethers based polyesters of this invention are those havingthe following Formula '1-5-b:

wherein is a member selected from the group comprising of p- ,phenylenegroup, m-phenylene group, 1,4-cyclohexylene group, 1,3-cyclohexylenegroup and the groups which are derived by substituting them with alkylgroups; q and r range zero to 3; A, X, G, m and u have the samesignificance defined theretofore; in the case that represents anaromatic ring, however, q and r may not be zero. And examples of thebishaloformate of dihydric alcohols (II-S-b) having the Formula 1-5-binclude, but are not be limted to, the bischloroformates andbisbromoformates of the following dihydric alcohols:

2,2-bis (4-hydroxycyclohexyl) -propane, (4,4-dihydroxy-dicyclohexyl)-methane,

' 1 4 1,1 -bis 4-hydroxycyclohexyl -ethane, 1, l-bis(4-hydroxycyclohexyl -propane, 1, 1-bis(4-hydroxycyclohexyl) -butane,1,1-bis (4-hydroxycyclohexyl) -p entane, 2,2-bis (4-hydroxycyclohexyl)-butane, 2,2-bis (4-hydroxycyclohexyl) -p entane,

' 2,2-bis(4-hydroxy-3-methyl-cyclohexyl)propane,

2,2-bis 4-hydroxy-2-methylcyclohexyl) -propane,

4,4'-dihydroxymethyl-bicyclohexane,

1,2-bis (4-hydroxymethyl-cyclohexyl) -ethane,

2,2-bis (4-hydroxymethylcyclohexyl) -p ro pane,

2,3-bis (4-hydroxymethyl-cyclohexyl) -butane,

2,3 -dimethyl-2, 3 -b is (4-hydroxymethylcyclohexyl) butane,

2,2-bis (4-hydroxymethylphenyl) -pro pane,

2,2-bis (4-fl-hydroxyethylphenyl -prop ane,

2,2-bis (4-hydroxypropylphenyl -prop ane,

1, l-bis (4-fl-hydroxyethylphenyl) -butane,

2,2-bis (4/i-hydroxyethylphenyl) -butane,

2,2-bis- (3 -methyl-4-B-hydroxyethylphenyl) -propane,

4,4'-di (p-hydroxyethyl -diphenylether,

4,4'-di fl-hydroxyethyl) -diphenylthioether,

4,4- fi-hydroxyethyl) -benzophenone,

bis (4-fi-hydroxy-ethyl-phenyl) -sulfone,

bis(3-,B-hydroxyethyl-phenyl) sulfone and the like.

Another class of the bishaloformates of dihydric alcols (II-5) havingthe general Formula 1-5 include, but are not limited to, thebischloroformates and bisbromoformates of the following dihydricalcohols;

1,3 -dihydroxycyclobutane,

1, 3 -dihydroxy-2,2,4,4-tetramethylcyclobutane,

2, 6-dihydroxy-decahydronaphthalene,

2,7-dihydroxy-decahydronaphthalene,

1, S-dihydroxy-decahydronaphathlene,

2,6-bis (hydroxymethyl -decahydronaphthalene,

2,7-bis (hydroxymethyl) -decahydronaphthalene,

1,5 -bis hydroxymethyl) -decahydronaphthalene,

1,4-bis(hydroxymethy1) -decahydronaphthalene,

1,4-bis- (hydroxymethyl) -bicyclo (2,2,2) octane,

dimethyloltricyclodecane,

and the like.

The strongly basic compounds (III) which are useful for preparing thepoly(hydroxyethers) based polyesters include alkali metal hydroxides,e.g. sodium hydroxide, potassium hydroxide mixture thereof, tertiaryamines represnted by the general Formula 5-1 and quaternary ammoniumsalts represented by the general Formula 5-2 disclosed hereinunder.

The basic catalysts (IV) which are useful for the preparation of thepoly(hydroxyethers) based polyesters of this invention include tertiaryamines (IV-1), quaternary ammonium salts (IV-2), and basic compoundscontaining phosphor, arsenic, antimony bismuth atom. And tertiary amines(IV-1) and quaternary ammonium salts (IV-2) are preferable for thepurpos of this invention.

The examples of the tertiary amines (IV-1) are those of the followingFormula 5-1:

, R1 N Rz Ra wherein R R and R are organic residues such as alkyl,hydroxyalkyl, aryl, aralkyl, alkaryl groups and the like, and preferablythose of which have up to 8 carbon atoms, and each of R R and R may bethe same or different, however R R and R may be joined together with anitrogen atom, and R and R may be joined together by carbon-carbon bondor joined together with oxygen or tertiary nitrogen atom. Preferredamong them include, but are not limited to, trialkyl amines, e.g.trimethyl .amine, triethyl amine, tri-n-propyl amine, tri-n-butyl amineand the like, trihydroxyalkyl amines, e.g. triethan01 amine,tri-isopropanol amine and the like, dialkylaryl amine, e.g. dimethylphenyl amine and the like, dialkyl-alkaryl amines, e.g. dirnethyl-benzylamine and the like, dialkyl-cycloalkyl amines, e.g. dimethyl-cyclohexylamine and the like, N-alkyl-piperadines, e.g. N-methyl piperadine andthe like, N-alkyl morpholines, e.g. N- methyl-morpholines.

The examples of the quaternary ammonium salts (IV-2) are those of thefollowing Formula -2.

wherein R R and R are organic residues such as alkyl, hydroxyalkyl aryl,alkaryl, aralkyl and th like, preferably those of which having up to 8carbon atoms, and each of R R and R may be the same or different,however R and R may be joined with carbon-carbon bond; R is an alkylgroup having up to 4 carbon atoms; A" is a monovalent anion.

And the examples of monovalent anion represented by A, there may bementioned halogen ion (for example, chloride ion, bromide ion and iodideion), alkyl sulfate ion (for example methyl sulfate ion and ethylsulfate ion), aromatic sulfonate ion (for example p-toluene sulfonateion and benzene sulfonate ion) and hydroxyl ion, however preferablemonovalent ion is halogen ion, methyl sulfate ion or hydroxyl ion.

As examples of particularly preferable quaternary ammonium salts (IV-2),there may be mentioned for example, tetramethylammonium chloride,tetramethylammonium bromide, tetraethylammonium iodide,tetramethyl-ammonium hydroxide, tetramethylamonium methyl sulfatetrimethyl-benzyl-ammonium chloride and trimethyl-benzyl-ammoniurnhydroxide.

As examples of preferable quaternary ammonium salt in which R and R arejoined together as a cyclic chain, there may be mentioned for examplN-dimethyl-piperidium chloride.

The examples of the tertiary phosphine, tertiary arsine, tertiaryantimony compound and tertiary bismuth compound which are included inthe basic compound (IV3) are represented by general Formula 53:

RI TZR" (5-3) RIII wherein M is phosphor, arsenic, antimony or bismuth,R, R" and R are selected from the group consisting of alkyl, aryl,alkaryl or aralkyl group having up to 8 carbon atoms, and each of R, R"and R" may be the same or different. And in the case that T is phosphor,R, R" and R may be joined together as a cyclic chain interrupted byphosphor atom.

Preferred among them include, but are not limited to, the following:trimethylphosphine, triethylphosphine, tributylphosphine,triphenylphosphine, tribenzylphospine, triethylenedihosphine,tributylarsine, tribenzylarsine, tributylantimony, triphenylantimony,tributylbismuth, and triphenylbismuth.

The process of this invention, for preparing the poly (hydroxyethers)based polyesters, can be conducted by admixing the poly(hydroxyethers)prepolymers (I) and from about 0.985 to about 1.05 moles, preferably onemole, of the dibasic acid halides (H), per mole of thepoly(hydroxyethers) prepolymers (I), together with catalytic amount ofthe basic catalysts (IV) in the presenc of one to more than oneequivalent of the strongly basic compounds (III), per equavalent of thephenolic hydroxy group of the poly(hpdroxyethers) prepolymer- (I). Andthe reaction of this invention can be carried in the presence of aninert diluent which is a solvent for one or more of the startingmaterials, and it is preferred to carry the reaction by admixing thesoluion which contains the poly(hydroxyethers) prepolymer (I) and thesolution which contains the dibasic acid halides (II) by vigorousstirring. The diluents which can be used in the method of this inventioninclude, among others the following:

(1) The solvents or dispersants for the poly(hydroxyethers) prepolymers(I) such as water, alcohols, e.g. methanol, ethanol, isopropanol,n-butanol, n-hexanol, tert.- butanol, benzyl-alcohol, cyclohexanol,ethylene glycol, and the like other hydroxylated compounds, e.g.ethylene glycol monomethyl ether, ethylene glycol monoethyl ether andthe like, aromatic hydrocarbons, e.g. benzene, xylene and the like,halogenated aromatic hydrocarbons, e.g. chlorobenzene and the like,halogenated aliphatic hydrocarbons, e.g. dichloromethane, chloroform,1,2-dichloroethane and the like, aliphatic ketones, e.g. acetone, methylethyl ketone, diethyl ketone and the like, ethers, e.g. diethyl ether,dioxane, tetrahydrofuran and the like, other polar solvents, e.g.dimethyl-formamide, dimethylphosphoramide and the like, and mixturethereof, and

(2) The solvents for the dibasic acid halides such as halogenatedaliphatic hydrocarbons as disclosed above, halogenated aromatichydrocarbons as disclosed above, nitrated aromatic hydrocarbons such asnitro benzene, nitrotoluene and the like, and mixture thereof, and thelike.

The reaction temperature for preparing the poly(hydroxyethers) basedpolyesters of this invention ranges from about 0 to about 50 C.,preferably. In the case that an acid dihalide or dicarboxylic acid isused as the dibasic acid halide (II), the reaction temperature is mostpreferably less than 35 C., in the case that a bis-haloformate ofdihydric compound is used as a dibasic acid halide (II), however, thereaction temperature is preferably less than 40 C., most preferably lessthan 25 C.

Careful control of the ratio of the poly(hydroxyether) prepolymer (I) tothe dibasic acid halides (II) in the reaction mixture is of greatimportance in order to prepare the product having the desiredproperties. Conducting the reaction by using the reaction mixture whichcontains more than 1.1 moles of the dibasic acid halides II), per moleof the poly(hydroxyethers) prepolymers (I), the terminating reactionoccurs, and the product having low molecular weight, poor chemicalresistance and poor impact strength is obtained inevitably. Andconducting the reaction by using the reaction mixture which containsless than 0.9 mole of the dibasic acid halides (II) per mole of thepoly(hydroxyethers) prepolymer (1), the terminating reaction occurs, andthe product having desired properties cannot be prepared.

To ones surprise, in the range of said conditions in this invention, anextremely high molecular weight linear polymer is produced on evidenceof the tests such as intrinsic viscosity and melt index, and thereaction between dibasic acid halide (II) and alcoholic hydroxyl groupsis utterly eliminated, and only reaction between dibasic acid halide(II) and the terminal phenolic hydroxyl groups advances selectively, andhigh molecular Weight linear polyester based on poly(hydroxyether) isproduced by connecting poly(hydroxyether) prepolymer mutually.

The poly(hydroxyether) based polyester of this invention hassufliciently high molecular weight and substantially linear structure,and has higher distortion temperature and stronger notched Izod impactstrength than those of well-known poly(hydroxyether) resin, and issuited for coating, laminating, film making and molding, and givescoating, lamination or film having lower gas permeability.

The invention will be better understood from the following examples.These examples are given for purposes of illustration only and theinvention is not to be considered as limited by the reactants andconditions described in the examples,

1 7 EXAMPLE 1 (a) Preparation of poly (hydroxyether) prepolymercomposition A The reaction vessel fitted with a sealed stirrer, athermometer and reflux condenser, was charged with the followingMaterial A. The reaction was carried out by stirring the Material A at30 C. for 30 hours. During this reaction, in every occasion that themixture became too viscous to stir, monochlorobenzene was added to themixture, until total weight of monochlorobenzene became to ten parts.

Thereafter, the resulting mixture was heated at a temperature of 7275C., for 6 hours and cooled to room temperature.

Material A: Parts by Wt. 2,2-bis(4-hydroxyphenyl)propane (1) 22.83Epichlorohydrin (0.95) 8.80 Tertiary butyl alcohol 23.0 Sodium hydroxide(1.05) 4.2 Water 16.1

The numbers in parentheses indicate mole-ratio. This appliescorrespondingly in the following cases.

(b) Preparation of poly(hydroxyether) based polyester The reactionvessel fitted with a stirrer and a thermometer, was charged with thefollowing Material B while stirring.

Then the following Material C was added to the reaction vessel undervigorous agitation. The reaction was carried out by stirring the mixtureof Material B and Material C for 30 minutes, thereafter hydrochloricacid was added, and the reaction was stopped. During the reaction, themixture was maintained at a temperature of 28-29 C.

The resulting mixture was washed five times with water, and the productwas precipitated by adding methanol, and separated from the mixture, anddried under vacuum.

EXAMPLE 2 (a) Preparation of poly(hydroxyether) prepolymer composition BThe reaction was carried out by the same method as that employed in theExample 1, except using the following Material A.

Thereafter, the resulting mixture was washed five times perature of 60C., for 6 hours, and cooled to room temperature.

Material A: Parts by wt. 2,2-bis(4-hydroxyphenyl) propane (1) 22.83Epichlorohydrin (0.9) 8.33 Tertiary butylalcohol 23.0 Sodium hydroxide(l) 4.0 Water 16.8

(b) Preparation of poly(hydroxyether) based polyester.

The reaction of poly(hydroxyether) prepolymer B and terephthaloyldichloride was carried out by the same method as that employed in theExample 1, except using the following Material B. and Material C.

Therefore, the resulting mixture was washed five times with water, andthe product was precipitated by adding methanol, and separated from themixture, and dried under vacuum.

The properties of product are shown hereinafter.

Material B: Parts by wt. Chloroform 400 Sodium hydroxide (0.1) 0.4 Water20 Trimethylbenzylammonium chloride 0.5

Poly(hydroxyether) prepolymer composition B (0.1)

whole volume by wt.

Material C: Parts by wt. Terephthaloyl dichloride (0.1) 2.03 Chloroform200 Properties of product:

Melt index 1.6 Heat distortion temperature (66 p.s.i.) C 108 Impactstrength, notched Izod (ft. lb./in., notch) 17.1

EXAMPLE 3 (a) Preparation of poly(hydroxyether) prepolymer composition CThe reaction was carried out by the same method as that employed in theExample 1, except using the following Material A.

Thereafter, the resulting mixture was heated at a temperature of 50 C.,for 6 hours, and cooled to room temperature.

Material A: Parts by wt. 2,2-bis(4-hydroxyphenyl) propane (1) 22.83Epichlohydrin (0.85) 7.87 Tertiary butylalcohol 23.0 Sodium hydroxide(0.95) 3.8 Water "a 16.8

(b) Preparation of poly(hydroxyether) based polyester The reaction ofpoly (hydroxyether) prepolymer C and iso-phthaloyl dichloride wascarried out by the same method as that employed in the Example 1, exceptusing the following Material B and Material C.

Thereafter, the resulting mixture was washed five times with water, andthe product was precipitated by adding methanol, and separated from themixture, and dried under vacuum.

The properties of product are shown hereinafter.

Material B: Parts by wt. Chloroform 400 Sodium hydroxide (0.2) 0.8 Water20 Trimethylbenzylammonium chloride 0.7

Poly(hydroxyether) prepolymer composition C (0.15)

19 EXAMPLE 4 of poly(hydroxyether) prepolymer The reaction was carriedout by the same method as that employed in the Example 1, except usingthe following Material A.

Thereafter, the resulting mixture was heated at a temperature of 40 C.,for hours, and cooled to room temperature. 10

Material A: Parts by wt. 2,2-bis(4-hydroxyphenyl) propane (1) 22.83'Epichlorohydrin (0.8) 7.41 Tertiary butylalcohol 23.0 Sodium hydroxide(0.9) 3.6 Water 17 (b) Preparation of poly(hydroxyether) based polyester20 The reaction of poly(hydroxyether) prepolymer D and terephthaloyldichloride was carried out by the same method as that employed in theExample 1, except using the following Material B and Material C.

Thereafter, the resulting mixture was washed five times with water, andthe product was precipitated by adding methanol, and separated from themixture, and dried under vacuum.

The properties of product are shown hereinafter.

Material B: Parts by wt. Chloroform 400 Sodium hydroxide (0.25) 1 Water20 Tetramethyl ammonium chloride 0.7 a Poly(hydroxyether) prepolymercomposition D (0.2) whole volume by wt.

Material C: Parts by wt.

Terephthaloyl dichloride (0.2) 4.05 Chloroform 200 Properties ofproduct:

Melt index 0.85

Heat distortion temperature (66 p.s.i.) C. 109 Impact strength, notchedIzod (ft. lb./in.

notch) 15.1

EXAMPLE 5 20 Material A: Parts by wt. 4,4'-dihydroxydiphenyl-ether (l)20.2 Epichlorohydrin (0.85) 7.87 Tertiary butylalcohol 23.0 Sodiumhydroxide (0.95) 3.8 Water 17.4

(b) Preparation of poly(hydroxyether) based polyester The reaction ofpoly(hydroxyether) prepolymer E and iso-phthaloyl dichloride was carriedout by the same method as that employed in the Example 1, except usingthe following Material B and Material C.

Thereafter, the resulting mixture was washed five times with water, andthe product was precipitated by adding methanol, and separated from themixture, and dried under vacuum.

The properties of product are shown hereinafter.

Material B: Parts by wt. Chloroform 400 Sodium hydroxide (0.2) 0.8 Water20 Trimethylbenzylammonium chloride 0.7

Poly(hydroxyether) prepolymer composition E (0.15) whole volume by wt.

Material C: Parts by wt. Iso-phthaloyl dichloride (0.15) 3.05 Chloroform200 Properties of product:

Melt index 0.21

Heat distortion temperature (66 p.s.i.) C. 155 Impact strength, notchedIzod (ft. lb./in.,

notch) 11.6

EXAMPLE 6 The poly(hydroxyether) prepolymer A B C and D that were shownin the Examples 1, 2, 3 and 4 respectively, were washed with dilutehydrochloric acid and washed six times with water to remove sodiumhydroxide and sodium chloride.

Then, 400 parts of chloroform, 20 parts of water, 0.5 parttrimethylbenzyl ammonium chloride and the same parts of sodium hydroxideas indicated in the Table I, were added to poly(hydroxyether) prepolymerand dissolved by agitation.

Chloroform solution of terephthaloyl dichloride was added to the mixtureand stirred for 30 minutes.

Thereafter the resulting mixture was washed five times with water, andthe product was purified by the same manner as that employed in theExample 1.

The results were shown in the Table I.

TABLE I.THE RELATIONS BETWEEN REACTION CONDITIONS OF POLY (HYDROXYETHER)PREPOLYMER AND ACID CHLORIDE, AND PROPERTIES OF PRODUCED POLYETHER-ESTERRE SINS Properties of produced resins Added volume of- ImpactTerephthaloyl strength, Sodium hydroxide dichloride Reaction Melt indexat Heat distortion notched Izod Klnd of poly(hydroxyether) temperature220 C. 44 p.s.i. temperature at (it. 1b.lin. prepolymer Part Mole PartMole (O.) (g./10 min.) 66 p.s.i. C.) notch) 0. 12 0. 03 l. 02 0. 005025-30 0. 34 101 12. 1 0. l2 0. 03 l. 12 0. 0055 25-30 6. 82 3. 5 0. 120. 03 2.03 0. 010 25-30 1. 45 107 15. 5 0 0 2. 03 0. 010 25-30 0. 1 Thisproduct did not substantially show plasticity 0. l2 0. 03 3. 05 0. 01525-30 0. 14. 7 0. 12 0.03 3. 05 0. 016 55-60 0. 1 This product did notsubstantially show plasticity 0. 16 0. 04 4. 05 O. 020 25-30 0. 77 11015. 3 0. 16 0. 04 3. 66 0. 018 25-30 14. 50 69 2. 5

Thereafter, the resulting mixture was heated at a temperature of 50 C.,for 6 hours, and cooled to room temperature. 75

1, 3, 5 and 7 in the Table I are the examples according to theinvention, and 2, 4, 6 and 8 are the examples for comparison.

21 EXAMPLE 7 (a) Preparation of poly(hydroxyether) prepolymercomposition Gr. Bisphenol A (0.10 mole) 22.83 Epichlorohydrin (0.075mole) 6.95 Sodium hydroxide (0.0825 mole) 3.5

(Note: purity of sodium hydroxide is 93%) Water 12.5Tertiarybutylalcohol 23.0

The above reaction mixture was stirred at a tempera- (b) Preparation ofpoly (hydroxyether) based polyester Then the following Material C wasadded to the reaction vessel under vigorous agitation. The reaction wascarried out by stirring the mixture of Material B and Material C for 30minutes, thereafter hydrochloric acid was added, and the reaction wasstopped. During the reaction, the mixture was maintained at atemperature of 28-29 C.

The resulting mixture was washed five times with water, and the productwas precipitated by adding meth- F g g s 255; g gfig g i at a anol, andseparated from the mixture, and dried under When the reaction wascompleted, 1.83 gr. of sodium 93: f d t h h f hydroxide (0.0425 mole)and 6.5 gr. of water was added 6 proper les 0 pro uc are 5 Own erema tothe resulting mature 90 Material B: Parts by wt. (b) Preparation ofpoly(hydroxyether) based polyester gggf 28 SolutionA.-Poly(hydroxyether) prepolymer was dis- Dimethylbenzyl amine 0,5solved in 400 gr. of chloroform, gr. of water and 0.7 Po1y(hydroxyether)prepolymer composition gr. of trimethyl-benzylammonium chloride as acatalyst. or A (0,5) hol ol m b wt,

Solution B.--6.33 gr. of the acid chloride which were ilililcatfidm 1nthe Table II, was dissolved 1n 200 gr. of Material 02 Parts by wt n lSolutions A and B were mixed and the mixture was Stirred vigor9llsly- 30o1oo--ooo1 oom 1.4

The reaction of poly(hydroxyether) prepolymer and acid chloride Wascarried out by stirring at a temperature of C. for minutes. Chloroform300 Thereafter the resulting mixture was washed five times Properties ofproduct: with water, and the product was purified by the same Heatdistortion temperature (66 p.s.i) C. 110 manner as that employed in theExample 1. 0 Impact strength, notched Izod (ft. lb./in.

The results were shown in the Table II. notch) 12.8

TABLE II Properties of polyether ester resin Impact Heat strength,distortion notched Izod Melt temp. (ft. 1b./in. No. Acid chloride indexC.) notch) 7-1 1,5-naphthoyl dichloride 0.75 12.2 7-2 2,6-naphthoyldichloride 0.73 111 11.9 7- ixture 0f1,5- and 2,6-naphthoyl 0. 88 30713. 5

dichloride.

EXAMPLE 8 EXAMPLE 9 (a) Preparation of poly(hydroxyether) prepolymerPreparation of p ly(hyf p p y composition A comP051on 2 temperature.

Material A: Parts by wt. 2,2-bis(4-hydroxyphenyl) propane (1) 22.83Epichlorohydrin (0.95) 8.80 Tertiary butyl alcohol 23.0 Sodium hydroxide(1.05) 4.2 Water 16.1

The numbers in indicate mole-ratio. This applies correspondingly in thefollowing cases.

The reaction was carried out by the same method as that employed in theExample 8, except using the following Material A.

Thereafter, the resulting mixture was heated at a temperature of 60 C.for 6 hours, and cooled to room temperature.

Material A: Parts by Wt. 2,2-bis(4-hydroxyphenyl) propane (l) 22.83Epichlorohydrin (0.9) 8.33 Tertiary butylalcohol 23.0 Sodium hydroxide(1) 4.0 Water 16.8

(b) Preparation of poly(hydroxyether) based polyester The reaction ofpoly(hydroxyether) prepolymer B and acid chloride was carried out by thesame method as that employed in the Example 8 except using the followingMaterial B and Material C.

Thereafter, the resulting mixture was washed five times with water, andthe product was precipitated by adding methanol, and separated from themixture, and dried under vacuum.

The properties of product are shown hereinafter.

Material B: Parts by wt. Chloroform 400 Sodium hydroxide (0.1) 0.4 Water20 Trimethylbenzylammonium chloride 0.5

Poly(hydroxyether) prepolymer composition B (0.1) whole volume by wt.

Material C:

010 o- -CH2 4: o1(0.1) 2. 93

Chloroform 300 Properties of product:

Heat distortion temperature (66 p.s.i.) C 111 Impact strength, notchedIzod (ft. lb./in.,

notch) 16.9

EXAMPLE (a) Preparation of poly(hydroxyether) prepolymer composition CThe reaction was carried out by the same method as that employed in theExample 8, except using the following Material A.

Thereafter, the resulting mixture was heated at a temperature of 50 C.,for 6 hours, and cooled to room temperature.

Material A: Parts by wt. 2,2-bis(4-hydroxyphenyl) propane (1) 22.83Epichlorohydrin (0.85) 7.87 Tertiary butylalcohol 23.0 Sodium hydroxide(0.95) 3.8 Water 17.4

(b) Preparation of poly(hydroxyether) based polyester Material B: Partsby wt. Chloroform 400 Sodium hydroxide (0.2) 0.8 WaterTrimethylbenzylammonium chloride 0.7

Poly(hydroxyether) prepolymer composition C (0.15) Whole volume by wt.

Material C: Parts by wt.

c10o -o-oH,oH2-0@-ooo1 Chloroform 350 Properties of product:

Heat distortion temperature (66 p.s.i.) C 111 Impact strength, notchedIzod (ft. 1b./in.,

notch) 18.3

EXAMPLE 11 (a) Preparation of poly(hydroxyether) prepolymer compositionD The reaction was carried out by the same method as that employed inthe Example 8, except using the following Material A.

Thereafter, the resulting mixture was heated at a temperature of 40 C.,for 10 hours, and cooled to roomtemperature.

Material A: Parts by wt. 2,2-bis(4-hydroxyphenyl) propane (1) 22.83Epichlorohydrin (0.8) 7.41 Tertiary butylalcohol 23.0 Sodium hydroxide(0.9) 3.6 Water 17 (b) Preparation of poly(hydroxyether) based polyesterThe reaction of poly(hydroxyether) prepolymer D and acid chloride wascarried out by the same method as that employed in the Example 8, exceptusing the following Material B and Material C.

Thereafter, the resulting mixture was washed five times with water, andthe product was precipitated by adding methanol, and separated from themixture, and dried under vacuum.

The properties of product is shown hereinafter.

Material B: Parts by wt. Chloroform 400 Sodium hydroxide (0.25) 1 Water20 Tetramethyl ammonium chloride 0.7

Poly(hydroxyether) prepolymer composition D (0.2) whole volume by wt.

Material C: Parts by Wt.

010 o-ooo o1 o.2) 5. 9

Chloroform 300 Properties of product:

Heat distortion temperature (66 p.s.i.) C-.. 107 Impact strength,notched Izod (ft. lb./in.,

notch) 17.9

EXAMPLE 12 (a) Preparation of poly(hydroxyether) prepolymer compositionE The reaction was carried out by the same method as that employed inthe Example 8, except using the following Material A.

Thereafter, the resulting mixture was heated at a temperature of 50 C.,for 6 hours, and cooled to room temperature.

Material A: Parts by wt. 4,4-dihydroxydiphenyl-ether (1) 20.2Epichlorohydrin (0.85) 7.87 Tertiary butylalcohol 23.0 Sodium hydroxide(0.95) 3.8 Water 16.8

(b) Preparation of poly(hydroxyether) based polyester The reaction ofpoly(hydroxyether) prepolymer E and acid chloride was carried out by thesame method as that employed in the Example 8, except using thefollowing Material B and Material C.

Thereafter, the resulting mixture was washed five times with water, andthe product was precipitated by adding methanol, and separated from themixture, and dried under vacuum.

The properties of product are shown hereinafter.

Material B: Parts by wt. Chloroform 400 Sodium hydroxide (0.2) 0.8 Water20 Trimethylbenzylammonium chloride 0.7

Poly(hydroxyether) prepolymer composition E (0.15 whole volume by wt.

. 25 Material C:

01o o- ---o o 01 0.15 4. 4s

Chloroform 300 Properties of product:

Heat distortion temperature (66 p.s.i.) C. 134 Impact strength, notchedIzod (ft. lb./in.,

notch) 19.1

EXAMPLE 13 (a) Preparation of poly(hydroxyether) prepolymer compositionA Material A: 7 Parts by wt. 2,2-bis(4-hydroxyphenyl)propane (0.1) 22.83Epichlorohydrin (0.095) 8.80 Tertiary butyl alcohol 23.0 Sodiumhydroxide (1.05) 4.2 Water 16.1

The numbers in indicate mole-ratio. This applies correspondingly in tothe following cases.

(b) Preparation of poly(hydroxyether) based polyester The reactionvessel fitted with a stirrer and a thermometer, was charged with thefollowing Material B while stirring.

Then the following Material C was added to the reaction vessel undervigorous agitation. The reaction was carried out by stirring the mixtureof Material B and Material C for 30 minutes, thereafter hydro chloricacid was added, and the reaction was stopped. During the reaction, themixture was maintained at a temperature of 0-5 C.

The resulting mixture was washed five times with water, and the productwas precipitated by adding methanol, and separated from the mixture, anddried under vacuum.

The properties of product are shown hereinafter.

Material B: Parts by wt. Chloroform 400 Water Dimethylbenzyl amine 0.5

Poly(hydroxyether) prepolymer (composition A (0.005) whole volume by wt.

Material C:

Hexahydro-iso-phthaloyl dichloride (0.005 1.05 Chloroform 200 Propertiesof product:

Melt index 1.12 Heat distortion temperature (66 p.s.i.) C. 95 Impactstrength, notched Izod (ft. lb./in.,

notch) 11.1

EXAMPLE 1-4 perature of C., for 6 hours, and cooled to room temperature.

Material A: Parts by wt. 2,2-bis(4-hydroxphenyl) propane (0.1) 22.83Epichlorohydrin (0.09) 8.33 Tertiary butylalcohol 23.0 Sodium hydroxide(0.1) 4.0 Water 16.8

(b) Preparation of poly(hydroxyether) based polyester The reaction ofpoly (hydroxyether) prepolymer B and hexahydroterephthaloyl dichloridewas carried out by the same method as that employed in the Example 13,except using the following Material B and Material C.

Thereafter, the resulting mixture was washed five times with water, andthe product was precipitated by adding methanol, and separated from themixture, and dried under vacuum.

The properties of product are shown hereinafter.

Material B: Parts by wt. Chloroform 400 Sodium hydroxide (0.01) 0.4Water 20 Trimethylbenzylammonium chloride 0.5

Poly(hydroxyether) prepolymer composition B 0.01) whole volume by wt.

Material C:

Hexahydroterephthaloyl dichloride (0.001) 2.09 Chloroform 200'Properties of product:

Melt index 1.9

Heat distortion temperature (66 p.s.i.) C. 101 Impact strength, notchedIzod (ft. 1b./in.,

notch) 18.2

EXAMPLE 15 (a) Preparation of poly(hydroxyether) prepolymer compositionC The reaction was carried out by the same method as that employed inthe Example 13, except using the following Material A.

Thereafter, the resulting mixture was heated at a temperature of 50 C.,for 6 hours, and cooled to room temperature.

Material A: Parts by wt. 2,2-bis(4-hydroxyphenyl) propane (0.1) 22.83Epichlorohydrin (0.085) 7.87 Tertiary butylalcohol 23.0 Sodium hydroxide(0.095) 3.8 Water 17.4

(b) Preparation of poly(hydroxyether) based polyester Material B: Partsby wt. Chloroform 400 Sodium hydroxide (0.02) 0.8 Water 20Trimethylbenzylammonium chloride 0.7

Poly(hydroxyether) prepolymer composition C (0.015) whole volume (byWt.)

lowing Material A.

Thereafter, the resulting mixture was heated at a temperature of 40 C,for hours, and cooled to room temperature.

Material A: Parts by wt. 2,2-bis(4-hydroxyphenyl) propane (0.1) 22.83Epichlorohydrin (0.08) 7.41 Tertiary butylalcohol 23.0 Sodium hydroxide(0.09) 3.6 Water 17 (b) Preparation f0 oly(hydroxyether based polyesterThe reaction of oly(hydroxyether) prepolymer D andhexahydroterephthaloyl dichloride was carried out by the same method asthat employed in the Example 13, except using the following Material Band Material C.

Thereafter, the resulting mixture was washed five times with water, andthe product was precipitated by adding methanol, and separated from themixture, and dried under vacuum.

The properties of product are shown hereinafter.

Material B: Parts by wt.

Chloroform 400 Sodium hydroxide (0.025) 1 Water 20 Tetramethyl ammoniumchloride 0.7

Poly(hydroxyether) prepolymer composition D (0.02) whole volume (by wt.)

28 EXAMPLE 17 (a) Preparation of oly(hydroxyether) propolymercomposition E The reaction was carried out by the same method as thatemployed in the Example 13, except using the following Material A.

Thereafter, the resulting mixture was heated at a temperature of 50 C.,for 6 hours, and cooled to room temperature.

Material A: Parts by wt. 4,4-dihydroxydiphenyl-ether (0.1) 20.2Epichlorohydrin (0.085) 7.87 Tertiary butylalcohol 23.0 Sodium hydroxide(0.095) 3.8 Water 17.4

(b) Preparation of poly (hydroxyether) based polyester The reaction ofpoly(hydroxyether) prepolymer E and hexahydro-isophthaloyl dichloridewas carried out by the same method as that employed in the Example 13,except using the following Material B and Material C.

Thereafter, the resulting mixture was washed five times with Water, andthe product was precipitated by adding methanol, and separated from themixture, and dried under vacuum.

The properties of product are shown hereinafter.

Material B: Parts by wt. Chloroform 400 Sodium hydroxide (0.02) 0.8Water 20 Tetramethyl ammonium chloride 0.7 Poly(hydroxyether) prepolymercomposition E (0.015) whole volume (by wt.)

Material C:

Hexahydro-iso-phthaloyl dichloride (0.015) 3.14 Chloroform 200Properties of product;

Melt index 0.35 Heat distortion temperature (66 p.s.i.) C. 149 Impactstrength, notched Izod (ft. 1b./in., notch) 12.3

EXAMPLE 18 The oly(hydroxyether) prepolymers A B C and D that were shownin the Examples 13, 14, 15 and 16 respectively, were washed with dilutehydrochloric acid and washed six times with water to remove sodiumhydroxide and sodium chloride.

Then, 400 parts of chloroform, 20 parts of water, 0.5 partstrimethylbenzyl ammonium chloride and the same parts of sodium hydroxideas indicated in the Table III, were added to poly(hydroxyether)prepolymer and dissolved by agitation.

Chloroform solution of hexahydroterephthaloyl dichloride was added tothe mixture and stirred for 30 minutes.

Thereafter the resulting mixture was Washed five times with water, andthe product was purified by the same manner as that employed in theExample 13.

TABLE III.THE RELATIONS BETWEEN REACTION CONDITIONS OFPOLYGIYDROXYETHER) PREPOLYMER AND ACID CHLORIDE, AND PROPERTIES OFPRODUCED POLYE'IHER-ESTER RESINS Added volume of- Properties of producedresins Hexahydro- Impact terephthaloylstrength, Sodium hydroxidedichloride Reaction Malt index at Heat distortion notched izod Kind ofpoly (hydroxyether) temperature 220 0.44 p.s.i. temperature at (it.lb./irt. prepolymer Part Mole Part Mole C.) (g./10 min.) 66 p.s.i. C.)notch) 0. l2 0. 03 1. 05 0. 0050 0-5 0. 44 98 13. 1 0. l2 0. 03 1. l5 0.0055 0-5 6. 10 80 3. 1 0. l2 0. 03 2. 09 0. 010 0-5 1. 104 15. 1

0 0 2. 09 0. 010 05 0. 1 This product did not substantially showplasticity 0. 12 0. 03 3. l4 0. 015 0-5 0. 91 107 15. 2 0. 12 0. 03 3.14 0. 015 45-55 0. 1 This product did not substantially show plasticity.0. l6 0. 04 4. l8 0. 020 0-5 0. 89 107 14. 2 0. 16 0. 04 3. 76 0. 018 0514. 21 63 2. 6

1, 3, and 7 in Table III are the examples according to the invention,and 2, 4, 6 and 8 are the examples for comparison.

- EXAMPLE 19 The reaction vessel fitted with a stirrer and athermometer, was charged with the following Material B while stirring.

Then the following Material C was added to the reaction, the mixture wasmaintained at a temperature of carried out by stirring the mixture ofMaterial B and Material C for 30 minutes, thereafter hydro chloric acidwas added, and the reaction was stopped. During the reaction, themixture was maintained at a temperature of 5-10 C.

The resulting mixture was washed five times with water, and the productwas precipitated by adding methanol, and separated from the mixture, anddried under vacuum. 1

The properties of product are shown hereinafter.

Material B: Parts by wt. Chloroform 400 Water 20 Dimethylbenzyl amine0.5

Poly(hydroxyether)prepolymer composition A (0.005) whole volume by wt.

Material C:

010 COCC1 (0.005) 1. 5

Chloroform 300 Properties of product:

Heat distortion temperature (66 p.s.i.) C.-- 107 Impact strength,notched Izod (ft. lb./in.,

notch) 12.5

EXAMPLE 20 (a) Preparation of poly(hydroxyether) prepolymer compositionA,

The reaction vessel fitted with a sealed stirrer, a thermometer andreflux condenser, was charged with the following Material A. Thereaction was carried out by stirring the Material A at 30 C. for 30hours. During this reaction, in every occasion that the mixture becametoo viscous to stir, monochlorobenzene was added to the mixture, untiltotal weight of monochlorobenzene became to ten parts.

Thereafter, the resulting mixture was heated at a temperature of 72-75C. for 6 hours and cooled to room temperature.

Material A: Parts by wt. 2,2-bis(4-hydroxyphenyl) propane (0.1) 22.83Epichlorohydrin (0.095) 8.80 Tertiary butylalcohol 23.0 Sodium hydroxide(0.105) 4.2 Water 16.1

The number in parentheses indicate mole-ratio. This appliescorrespondingly in the following cases.

(b) Preparation of poly(hydroxyether) based polyester The reactionvessel fitted with a stirrer and a thermometer, was charged with thefollowing Material B while stirring,

Then the following Material C was added to the reaction vessel undervigorous agitation. The reaction was carried out by stirring the mixtureof Material B and Material C for 30 minutes, thereafter hydrochloricacid Was added, and the reaction was stopped. During the reaction, themixture was maintained at a temperature of 0-5 C.

The resulting mixture was washed five times with water, and the productwas precipitated by adding methanol, and separated from the mixture, anddried under vacuum.

30 The properties of product are shown hereinafter.

Material B: Parts by wt. Chloroform 400 Water 20 Dimethylbenzyl amine0.5

Poly(hydroxyether) prepolymer composition A,

(0.005 whole volume by wt.

Material C: Parts by wt. p-Phenylene diacetyl dichloride (0.005) 1.15Chloroform 200 Properties of product:

Melt index 1.25 Heat distortion temperature (66 p.s.i.) C. 93 Impactstrength, notched Izod (ft. lb./in.,

notch) 10.6

EXAMPLE 21 (a) Preparation of poly(hydroxyether) prepolymer compositionB The reaction was carried out by the same method as that employed inthe Example 20, except using the following Material A.

Thereafter, the resulting mixture was heated at a temperature of 60 C.,for 6 hours, and cooled to room temperature.

Material A: Parts by wt. 2.2-bis(4-hydroxyphenyl) propane (0.1) 22.83Epichlorohydrin (0.09) 8.33 Tertiary butylalcohol 23.0 Sodium hydroxide(0.1) 4.0 Water 16.8

(b) Preparation of poly(hydroxyether) based polyester The reaction ofpoly(hydroxyether) prepolymer B and p-phenylene dipropyl dichloride wascarried out by the same method as that employed in the Example 20,except using the following Material B and Material C.

Thereafter, the resulting mixture was washed five times With water, andthe product Was precipitated by adding methanol, and separated from themixture, and dried under vacuum.

The properties of product are shown hereinafter.

EXAMPLE 22 (a) Preparation of poly(hydroxyether) prepolymer compositionC The reaction was carried out by the same method as that employed inthe Example 20, except using the following Material A.

Thereafter, the resulting mixture was heated at a temperature of 50 C.for 6 hours, and cooled to room temperature.

31 Material A: Parts by Wt. 2,2-bis)-4-hydroxyphenyl) propane (0.1)22.83 Epichlorohydrin (0.085 7.87 Tertiary butylalcohol 23.0 Sodiumhydroxide (0.095) 3.8 Water 17.4

(b) Preparation of poly(hydroxyether) based polyester The reaction ofpoly(hydroxyether) prepolymer C and p-phenylene diacetyl dichloride wascarried out by the same method as that employed in the Example 20,except using the following Material B and Material C.

Thereafter, the resulting mixture was washed five times with water, andthe product was precipitated by adding methanol, and separated from themixture, and dried under vacuum.

The properties of product are shown hereinafter.

Material B: Parts by wt. Chloroform 400 Sodium hydroxide (0.02) 0.8Water 20 Trimethylbenzylammonium chloride 0.7 Poly(hydroxyet'her)prepolymer composition C (0.015) whole volume by wt.

Material C:

p-Phenylene diacetyl dichloride (0.015) 3.47 Chloroform 200 Propertiesof product:

Melt index 2.6

Heat distortion temperature (66 p.s.i.) C. 96

Impact strength, notched Izod (ft. lb./in.,

notch) 3.2

EXAMPLE 23 (a) Preparation of poly(hydroxyether) prepolymer compositionD The reaction was carried out by the same method as that employed inthe Example 20, except using the following Material A.

Thereafter, the resulting mixture was heated at a temperature of 40 C.,for hours, and cooled to room temperature.

Material A: Parts by wt. 2,2-bis(4-hydroxyphenyl) propane (0.1) 22.83Epichlorohydrin (0.08) 7.41 Tertiary butylalcohol 23.0 Sodium hydroxide(0.09) 3.6 Water 17 (b) Preparation of poly(hydroxyether) basedpolyester The reaction of poly (hydroxyether) prepolymer D andp-phenylene diacetyl dichloride was carried out by the same method asthat employed in the Example 20, except using the following Material Band Material C.

Thereafter, the resulting mixture was washed five times with water, andthe product was precipitated by adding methanol, and separated from themixture, and dried under vacuum.

The properties of product are shown hereinafter.

Material B: Parts by wt. Chloroform 400 Sodium hydroxide (0.025) 1 Water20 Tetramethylammonium chloride 0.7

Poly(hydroxyether) prepolymer composition D,

(0.02) Whole volume by wt.

32 Material C:

p-Phenylene diacetyl dichloride (0.02) 4.62 Chloroform 200 Properties ofproduct:

Melt index 1.29

Heat distortion temperature (66 p.s.i.) C.-- 101 Impact strength,notched Izod (ft. lb./in.,

notch) EXAMPLE 24 (a) Preparation of poly(hydroxyether) prepolymercomposition E The reaction was carried out by the same method as thatemployed in the Example 20, except using the following Material A.

Thereafter, the resulting mixture was heated at a temperature of 50 C.,for 6 hours, and cooled to room temperature.

Material A: Parts by wt. 4,4'-dihydroxydiphenyl-ether (0.1) 20.2Epichlorohydrin (0.085) 7.87 Tertiary butylalcohol 23.0 Sodium hydroxide(0.095) 3.8 Water 17.4

(b) Preparation of poly (hydroxyether) based polyester The reaction ofpoly(hydroxyether) prepolymer E and p-phenylene diacetyl dichloride wascarried out by the same method as that employed in the Example 20,except using the following Material B and Material C.

Thereafter, the resulting mixture was washed five times with water, andthe product was precipitated by adding methanol, and separated from themixture, and dried under vacuum.

The properties of product are shown hereinafter.

Material B: Parts by wt. Chloroform 400 Sodium hydroxide (0.02) 0.8Water 20 Trimethylbenzylammonium chloride 0.7

Poly(hydroxyether) prepolymer composition E (0.015 Whole volume by wt.

Material C:

p-Phenylene diacetyl dichloride (0.015 3.74 Chloroform 200 Properties ofproduct:

Melt index 0.45

Heat distortion temperature (66 p.s.i.) C. Impact strength, notched Izod(ft. 1b./in.,

notch) 12.5

EXAMPLE 25 The poly(hydroxyether) prepolymer A B C and D that was shownin the Example 20, 21, 22 and 23 respectively, were washed with dilutehydrochloric acid and washed six times with water to remove sodiumhydroxide and sodium chloride.

Then, 400 parts of chloroform, 20 parts of water, 0.5 parttrimethylbenzyl ammonium chloride and the same parts of sodium hydroxideas indicated in the Table IV, were added to poly(hydroxyether)prepolymer and dissolved by agitation.

Chloroform solution of p-phenylene diacetyl dichloride was added to themixture and stirred for 30 minutes.

Thereafter the resulting mixture was washed five times with water, andthe product was purified by the same manner as that employed in theExample 20.

The results were shown in the Table IV.

TABLE IV.THE RELATIONS BETWEEN REACTION CONDITIONS OF POLY(HYDROXYETHER)PREPOLYMER AND ACID CHLORIDE, AND PROPERTIES OF PRODUCEDPOLYETHER-ESTER. RESINS Added volume of- Properties of produced resinsSodium p-Phenylene diacetyl Impact strength, hydroxide dichlorideReaction Melt index at Heat distortion notched izod Kind ofpoly(hydroxytemperature 220 C. 44 p.s.i. temperature at (it. lb./in.,ether) prepolymer Part Mole Part Mole C.) (g./10 min.) 66 p.s.i. C.)notch) 0 0 2. 03 0. 010 0-5 0. 1 This product did not substantially showplasticity 0. 12 0. 03 3. 0. 015 0-5 0. 98 103 14. 8 0. 12 0.03 3. 05 0.015 45-55 0. 1 This product did not substantially show plasticity 0. 160. 04 4. 05 0. 020 0-5 0. 90 102 15. 1 0. l6 0. 04 3. 66 0. 018 0-5 14.35 60 2. 0

1, 3, 5 and 7 in the Table IV are the examples accordfigg ggj 300 ing tothe invention, and 2, 4, 6 and 8 are the examples p p a for com arisonHeat distortion temperature (66 p.s.i.) C. 106

p Impact strength, notched Izod (ft. lb./in.,

EXAMPLE 26 notch) 16.2 The reaction vessel fitted with a stirrer and athermometer, was charged with the following Material B while EXAMPLE 28stirring.

Then the following Material 0 was added to the re- The reactlon f P y( yp p y 4 and action vessel under vigorous agitation. The reaction wascarried out by stirring the mixture of Material B and Material C for 30minutes, thereafter hydrochloric acid was added, and the reaction wasstopped. During the reaction, the mixture was maintained at atemperature of 5-10 C.

The resulting mixture was washed five times with water, and the productwas precipitated by adding methanol, and separated from the mixture, anddried under vacuum.

The properties of product are shown hereinafter.

Material B: Parts by wt. Chloroform 400 Water 20 Dimethylbenzyl amine0.5

Poly(hydroxyether) prepolymer composition A;

(0.005) whole volume by Wt.

Material C:

010 O-OHz-QQ-Cfir-O 0 C1(0.005) 1. 5

Chloroform 300 Properties of product:

Heat distortion temperature (66 p.s.i.) C. 105 Impact strength, notchedIzod (ft. 1b./in.,

notch) 13.1

EXAMPLE 27 Material B: Parts by wt. Chloroform 400 Sodium hydroxide 0.4Water 20 Trimethylbenzylammonium chloride 0.5

Poly(hydroxyether) prepolymer composition B (0.01) whole volume by wt.

Material C:

010 o-om-Q-om-Q-cm-o 0 or acid chloride was carried out by the samemethod as that employed in the Example 26, except using the followingMaterial B and Material C.

Thereafter, the resulting mixture was washed five times with water, andthe product was precipitated by adding methanol, and separated from themixture, and dried under vacuum.

The properties of product are shown hereinafter.

EXAMPLE 29 The reaction of poly(hydroxyether) prepolymer D and acidchloride was carried out by the same method as that employed in theExample 26, except using the following Material B and Material C.

Thereafter, the resulting mixture was washed five times with water, andthe product was precipitated by adding methanol, and separated from themixture, and dried under vacuum.

The properties of product are shown hereinafter.

Material B:

Parts by wt. Chloroform 400 Sodium hydroxide (0.025) 1 Water 20Tetramethylammonium chloride 0.7 Poly(hydroxyether) prepolymercomposition D,

(0.02) whole volume by wt. Material C:

O10 C-CHzQ-OQ-CHz-C 0 Cl 35 Chloroform 300 Properties of product:

Heat distortion temperature (66 p.s.i.) C. 106 Impact strength, notchedIzod (ft. lb./in., notch) 5 EXAMPLE 30 The reaction ofpoly(hydroxyether) prepolymer E and acid chloride was carried out by thesame method as that employed in the Example 26, except using thefollowing Material B and Material C.

Thereafter, the resulting mixture was washed five times with water, andthe product was precipitated by adding methanol, and separated from themixture, and dried under vacuum.

The properties of product are shown hereinafter.

Material B:

Parts by wt. Chloroform 400 Sodium hydroxide (0.02) 0.8 WaterTrimethylbenzylammonium chloride 0.7

Poly(hydroxyether) prepolymer composition E (0.015) whole volume by wt.Material C:

010 o-onQ-o-Q-orn-o o 01 Chloroform Properties of product:

Heat distortion temperature (66 p.s.i.) C. 124 Impact strength, notchedIzod (ft. lb./in.,

notch) 16.2

EXAMPLE 31 (21) Preparation of poly(hydroxyether) prepolymer compositionA The reaction vessel fitted with a sealed stirrer, a thermometer andreflux condenser, was charged with the following Material A. Thereaction was carried out by stirring the Material A at 30 C. for 30hours. During this reaction, in every occasion that the mixture becametoo viscous to stir, monochlorobenzene was added to the mixture, untiltotal weight of monochlorobenzene became to ten parts.

Thereafter, the resulting mixture was heated at a temperature of 72-75C., for 6 hours and cooled to room temperature.

Material A: Parts by wt. 2,2-bis(4-hydroxyphenyl propane (1) 22.83Epichlorohydrin (0.95) 8.80 Tertiary butyl alcohol 23.0 Sodium hydroxide(1.05) 4.2 Water 16.1

The numbers in indicate mole-ratio. This applies correspondingly to thefollowing cases.

(b) Preparation of bischloroformate of- 2,2-bis(4- hydroxyphenyl)propane is a by-product, was separated by filtering.

a an... 1100 Aicfillml at 50 f. under nressurg of mm. Hg at first and of1 mm. Hg absolute pressure thereafter. The distillation was carried outuntil all of the solvent evaporated.

Thus, bischloroformate of 2,2-bis (4-hydroxyphenyl) propane wasobtained.

This product was recrystallized from methylenechloride and purified.

(0) Preparation of poly(hydroxyether) based polyester The reactionvessel fitted with a stirrer and a thermometer, was charged with thefollowing Material B While stirring.

Then the following Material C was added to the reaction vessel undervigorous agitation. The reaction was carried out by stirring the mixtureof Material B and Material C for 30 minutes, thereafter hydrochloricacid was added, and the reaction was stopped. During the reaction, themixture was maintained at a temperature of 5-9 C.

The resulting mixture was washed five times with water, and the productwas precipitated by adding methanol, and separated from the mixture anddried under vacuum.

The properties of product are shown hereinafter.

Material B: Parts by wt. Chloroform 400 Water 20 Dimethylbenzyl aminePoly(hydroxyether) prepolymer composition A (0.05) whole volume by wt.

(a) Preparation of poly(hydroxyether) prepolymer composition B Thereaction was carried out by the same method as that employed in theExample 31, except using the following Material A.

Thereafter, the resulting mixture Was heated at a temperature of 60 C.,for 6 hours, and cooled to room temperature.

Material A: Parts by wt. 2,2-bis(4-hydroxyphenyl) propane (1) 22.83Epichlorohydrin (0.9) 8.33 Tertiary butylalcohol 23.0 Sodium hydroxide(1) 4.0 Water 16.8

(b) Preparation of poly(hydroxyether) based polyester The reaction ofpoly(hydroxyether) prepolymer B and bischloroformate ofbis(4-hydroxyphenyl) ether was carried out by the same method as thatemployed in the Example 31, except using the following Material B andMaterial C.

Thereafter, the resulting mixture was washed five times with water, andthe product was precipitated by adding methanol, and separated from themixture, and dried under vacuum.

The properties of product are shown hereinafter.

Material B: Parts by wt. Chloroform 400 Sodium hydroxide (0.1) 0.4 Water20 Trimethylbenzylammonium chloride 0.5

Poly(hydroxyether) prepolymer composition B (0.1) whole volume by wt.

37 Material C:

Bischloroformate of bis(4-hydroxyphenyl) ether (0.1) 3.27 Chloroform 200Properties of product:

Melt index 1.12

Heat distortion temperature (66 p.s.i.) C. 111 Impact strength, notchedizod (ft. lb./in.,

notch) 17.1

EXAMPLE 33 (a) Preparation of poly(hydroxyether) prepolymer compositionC The reaction was carried out by the same method as that employed inthe Example 31, except using the following Material A.

Thereafter, the resulting mixture was heated at a temperature of 50 C.,for 6 hours, and cooled to room temperature.

Material A: Parts by wt. 2,2-bis(4-hydroxyphenyl) propane (1) 22.83Epichlorohydrin (0.85) 7.87 Tertiary butylalcohol 23.0 Sodium hydroxide(0.95) 3.8 Water 17.4

(b) Preparation of poly(hydroxyether) based polyester Material B: Partsby wt. Chloroform 400 Sodium hydroxide (0.2) 0.8 Water 2OTrimethylbenzylammonium chloride 0.7

Poly(hydroxyether) prepolymer composition C (0.15) whole volume by wt.

Material C:

Bischloroformate of bis( Lhydroxyphenyl) sulfone (0.15) 5.63 Chloroform200 Properties of product:

Melt index 0.48

Heat distortion temperature (66 p.s.i.) C. 121 Impact strength, notchedIzod (ft. lb./in.

notch) 13 1 EXAMPLE 34 (a) Preparation of poly(hydroxyether) prepolymercomposition D The reaction was carried out by the same method as thatemployed in the Example 31, except using the following Material A.

Thereafter, the resulting mixture was heated at a temperature of 40 C.,for hours, and cooled to room temperature.

Material A: I Parts by Wt. 2,2-bis(4-hydroxyphenyl) propane (1) 22.83Epichlorohydrin (0.8) 7.41 Tertiary butylalcohol 23 .0 Sodium hydroxide(0.9) 3.6 Water 17 (b) Preparation of poly(hydroxyether) based polyesterThe reaction of poly(hydroxyether) prepolymer D and bischloroformate ofbis (4-hydroxyphenyl) methane was carried out by the same method as thatemployed in the Example 31, except using the following Material B andMaterial C.

Thereafter, the resulting mixture was washed five times with water, andthe product was precipitated by adding methanol, and separated from themixture, and dried under vacuum.

The properties of product are shown hereinafter.

Material B: Parts by wt. Chloroform 400 Sodium hydroxide (0.25 1 Water20 Tetramethyl ammonium chloride 0.7

(Polyhydroxyether) prepolymer composition D (0.2) whole volume by wt.

Material C:

Bischloroformate of bis(4-hydroxyphenyl) methane (0.2) 6.50 Chloroform200 Properties of product:

Melt index 1.02 Heat distortion temperature (66 p.s.i.) C. 109 Impactstrength, notched Izod (ft.

1b./inch., notch) 15.1

EXAMPLE 35 Preparation of poly(hydroxyether) prepolymer composition EThe reaction was carried out by the same method as that employed in theExample 31, except using the following Material A.

Thereafter, the resulting mixture was heated at a temperature of 50 C.,for 6 hours, and cooled to room tem perature.

Material A: Parts by wt. 4,4'-dihydroxydiphenyl ether (1) 20.2B-Methyl-epichlorohydrin (0.85) 9.14 Tertiary butyalcohol 23.0 Sodiumhydroxide (0.95) 3.8 Water 17.4

(b) Preparation of poly(hydroxyether) based polyester The reaction ofpoly(hydroxyether) prepolymer E and bischloroformate of resorcinol wascarried out by the same method as that employed in the Example 31,except using the following Material B and Material C.

Thereafter, the resulting mixture was washed five times with water, andthe product was precipitated by adding methanol, and separated from themixture, and dried under vacuum.

The properties of product are shown hereinafter.

Material B: Parts by wt. Chloroform 400 Sodium hydroxide (0.2) 0.8 Water20 Trimethylbenzylammonium chloride 0.7

Poly(hydroxyether) prepolymer composition E, (0.15) whole volume by wt.

Material C:

Bischloroformate of resorcinol (0.1.5) 3.53 Chloroform 200 Properties ofproduct:

Melt index 0.3 1

Heat distortion temperature (66 p.s.i.) C. 149 Impact strength, notchedIzod (ft.

lb./in., notch) 13.9

39 40 EXAMPLE 36 Solution B.6.33 gr. (0.025 mole) of the acid chloridewhich were indicated in the Table VI, was dissolved in 200 gr. ofchloroform.

Solutions A and B were mixed and the mixture was stirred vigorously.

The reaction of poly(hydroxyether) prepolymer and acid chloride wascarried out by stirring at a temperature of 5 C. for 50 minutes.

Thereafter the resulting mixture was washed five times with water, andthe product was purified by the same manner as that employed in theExample 31.

The results were shown in the Table VI.

The poly(hydroxyether) prepolymer A B C and D that was shown in theExample 31, 32, 33 and 34 respectively, were washed with dilutehydrochloric acid and washed six times with water to remove sodiumhydroxide 5 and sodium chloride.

Then, 400 parts of chloroform, 20 parts of water,.0.5 parttrimethylbeuzyl ammonium chloride and the same parts of sodium hydroxideas indicated in the Table V, were added to poly(hydroxyether) prepolymerand disl solved by agitation.

Chloroform solution of bischloroformate of 2,2-bis TABLE VI Propertiesof polyether ester resin Impact Heat strength, distortion notched izodMelt temp. (it. 1b./in No. Heloformate index C.) notch) 37-1Bischloroiormate of 1,5-di- 0.86 100 13. 2

hydroxynaphthalene. 37-2 Bischloroiormate of 2,6-d1- 0.82 110 12. 5

hydroxynaphthalene. 37-3 Mixture of bisehloroiormate of 0. 95 106 14. 1

1,5- and 2,6-dihydroxynaphthalene.

(4-hydroxyphenyl) propane was added to the mixture EXAMPLE 38 andstirred for 30 minutes.

Thereafter the resulting mixture was washed five times 30 with water,and the product was purified by the same manner as that employed in theExample 31. The reaction vessel fitted with a sealed stirrer, a ther-The results were shown in the Table V. mometer and reflux condenser, wascharged with the (a) Preparation of poly(hydroxyether) prepolymercomposition A TABLE V.THE RELATIONS BETWEEN REACTION CONDITIONS OFPOLY(HYDROXYETHER)PREPOLYMER AND ACID CHLORIDE. AND PROPERTIES OFPRODUCED POLYETHER-ES'IER RESINS Added volume of- Properties of producedresins Bischloroiormete of Impact; Sodium 2,2-bis(4-hydroxy- Melt indexat Heat distortion strength, hydroxide phenyl propane Reaction 220 0.,44 p .s.i. temperature at notched izod Kind of poly hydroxyothertemperature (g./10 mm.) 66 p.s.i. C.) (it. 1b./in. prepolymer Part MolePart Mole C.) notch) 0 0 3. 53 0. 010 5-10 0. 1 This product did notsubstantially show plasticity 0. l2 0. O3 5. 0. 015 5-10 1. 16 108 18. 10. 12 0. 03 5. 30 0. 015 55-60 0. 1 This product did not substantiallyshow plasticity 0. 16 0. 04 7. 06 0. 020 5-10 1. 12 108 21. 0 0. 16 0.O4 6. 0. 018 5-10 19 30 66 1. 9

l, 3, 5 and 7 in the Table V are the examples accordfollowing MaterialA. The reaction was carried out by ing to the invention, and 2, 4, 6 and8 are the examples stirring the Material A at 30 C. for 30 hours. Duringthis for Comparison reaction, in every occasion that the mixture becametoo EXAMPLE 37 viscous to stir, monochlorobenzene was added to the mixh1 ture, until total weight of monochlorobenzene became to (a)Preparation of po1y(hy y P P Y t t COITIPOSIUOH Thereafter, theresulting mixture was heated at a temperature of 72-75 C., for 6 hoursand cooled to room Bispheuol A (0-10 mole) 22'83 temperature,Epichlorohydriu (0.075 mole) 6.95 Sodium hydroxide (0.0825 mole) 3.5 90Material Ar Parts by wt. pdddy dd dddddd ddddddddd d 9% fiiitiioitiiiiii ffiiiiiffi 5133 Water Tertiary butyl alcohol 23.0 1 1 3-0 Sodiumhydroxide (1.05) 4.2 Th above reaction mixture was stirred at a te pe 05Water 16,1 ature of 35 C. for 30 hours and thereafter heated at atemperature of 74-75 C. for 7 hours stirring. The numbers. In lndlcate{Hole-T2100 Thls pp When the reaction was completed, 1.83 gr. of sodiumcorrespondlngly 111 the following caseshydroxrde (0.0425 mole) and 6.5gr. of water was added (b) Preparation of polymydroxyether) basedpolyester to the resulting mixture. Th 1 fi d h e reaction vesse tte wita stirrer and a ther- (b) Preparatlon of Polymydmxyethfl) basedpolyester mometer, was charged with the following Material B SolutionA.Poly(hydroxyether) prepolymer was diswhile stirring. solved in 400 gr.of chloroform, 20 gr. of water and 0.7 gr. Then the following Material Cwas added to the reacof trimethyl-benzylammonium chloride as a catalyst.75 tion vessel under vigorous agitation. The reaction was

